To
define and control the parameters which impact headspace solid-phase
microextraction (HS-SPME), it is important to reach the highest level
of reproducibility. The present study aims to assess, for the first
time, the effect of fiber–sample distance during HS-SPME in
pre-equilibrium conditions. Analyses were primarily performed on mixtures
of standard volatiles compounds (alkanes, alcohols, organic acids)
designed in our lab and then on various food matrices (wine, chicken,
cheese, tea), repeating already published experiments. Extractions
were performed varying fiber penetration depths (10–60 mm)
at different times (10–60 min) and temperatures of extraction
(30–80 °C). The study revealed that variation of the
distance between the fiber and the sample into the vial clearly impacts
the results obtained during HS-SPME when conditions are such that
no equilibrium is reached in HS. For example, in wine analysis, the
percentage of octanoic acid at 80 °C was higher at 40 mm (7.5
± 0.2%) than that at 20 mm (4.4 ± 0.3%). Moreover, regardless
of the extraction temperature, the lower the time of extraction, the
stronger the dependence on the fiber–sample distance. Indeed,
at 60 °C, the obtained response factors for octadecane at 20
and 40 mm of fiber penetration were 21.8 and 44.5, respectively, after
10 min of extraction, 54.1 and 71.0 after 30 min, and 79.4 and 82.4
after 60 min of extraction. The analyses have been here corroborated
by a theoretical model based on the diffusion equation. Therefore,
to improve the method robustness during HS-SPME studies, we suggest
specifying the fiber penetration depth or the fiber–sample
distance with the other parameters of extraction.